scholarly journals Ethylene oligomerization in metal–organic frameworks bearing nickel(ii) 2,2′-bipyridine complexes

2017 ◽  
Vol 201 ◽  
pp. 351-367 ◽  
Author(s):  
Miguel I. Gonzalez ◽  
Julia Oktawiec ◽  
Jeffrey R. Long
Keyword(s):  
Crystal Structure ◽  
Catalytic Activity ◽  
Single Crystal ◽  
Metal Organic Frameworks ◽  
Ethylene Oligomerization ◽  
Confinement Effects ◽  
Polymer Formation ◽  
Metal Organic ◽  
Selectivity Control ◽  
Nickel Species

The metal–organic frameworks Zr6O4(OH)4(bpydc)6 (1; bpydc2− = 2,2′-bipyridine-5,5′-dicarboxylate) and Zr6O4(OH)4(bpydc)0.84(bpdc)5.16 (2; bpdc2− = biphenyl-4,4′-dicarboxylate) were readily metalated with Ni(DME)Br2 (DME = dimethoxyethane) to produce the corresponding metalated frameworks 1(NiBr2)6 and 2(NiBr2)0.84. Both nickel(ii)-containing frameworks catalyze the oligomerization of ethylene in the presence of Et2AlCl. In these systems, the pore environment around the active nickel sites significantly influences their selectivity for formation of oligomers over polymer. Specifically, the single-crystal structure of 1(NiBr2)5.64 reveals that surrounding metal–linker complexes enforce a steric environment on each nickel site that causes polymer formation to become favorable. Minimizing this steric congestion by isolating the nickel(ii) bipyridine complexes in the mixed-linker framework 2(NiBr2)0.84 markedly improves both the catalytic activity and selectivity for oligomers. Furthermore, both frameworks give product mixtures that are enriched in shorter olefins (C4–10), leading to deviations from the expected Schulz–Flory distribution of oligomers. Although these deviations indicate possible pore confinement effects on selectivity, control experiments using the nickel-treated biphenyl framework Zr6O4(OH)4(bpdc)6(NiBr2)0.14 (3(NiBr2)0.14) reveal that they likely arise at least in part from the presence of nickel species that are not ligated by bipyridine within 1(NiBr2)5.64 and 2(NiBr2)0.84.

scholarly journals New Microporous Lanthanide Organic Frameworks. Synthesis, Structure, Luminescence, Sorption, and Catalytic Acylation of 2-Naphthol

Molecules ◽  
2020 ◽  
Vol 25 (13) ◽  
pp. 3055
Author(s):  
Dana Bejan ◽  
Lucian Gabriel Bahrin ◽  
Sergiu Shova ◽  
Narcisa Laura Marangoci ◽  
Ülkü Kökҫam-Demir ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Catalytic Activity ◽  
Single Crystal ◽  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
X Ray ◽  
Surface Areas ◽  
Potential Applications ◽  
Metal Organic ◽  
Solvothermal Conditions

New metal-organic frameworks (MOF) with lanthanum(III), cerium(III), neodymium(III), europium(III), gadolinium(III), dysprosium(III), and holmium(III)] and the ligand precursor 1,3,5-tris(4-carboxyphenyl)-2,4,6-trimethylbenzene (H3L) were synthesized under solvothermal conditions. Single crystal x-ray analysis confirmed the formation of three-dimensional frameworks of [LnL(H2O)2]n·xDMF·yH2O for Ln = La, Ce, and Nd. From the nitrogen sorption experiments, the compounds showed permanent porosity with Brunauer-Emmett-Teller (BET) surface areas of about 400 m2/g, and thermal stability up to 500 °C. Further investigations showed that these Ln-MOFs exhibit catalytic activity, paving the way for potential applications within the field of catalysis.

Controlled Growth of the Non-centrosymmetric Zn(3-ptz)2 and Zn(Oh)(3-ptz) Metal-organic Frameworks

2019 ◽  
Author(s):  
javier enriquez ◽  
Ignacio Chi-Duran ◽  
Carolina Manquian ◽  
Felipe Herrera ◽  
Ruben Fritz ◽  
...  
Keyword(s):  
Single Crystal ◽  
Nonlinear Optical ◽  
Metal Organic Frameworks ◽  
Molar Ratio ◽  
Thermal Synthesis ◽  
Small Crystals ◽  
Alkaline Environments ◽  
Potential Applications ◽  
Metal Organic ◽  
Long Rod

Non-centrosymmetric single-crystal metal-organic frameworks (MOF) are promising candidates for phase-matched nonlinear optical communication, but typical hydrothermal synthesis produces small crystals with relatively low transmittance and poor phase matching. We study the effect of the metal-to-ligand molar ratio and reaction pH on the hydro-thermal synthesis of the non-centrosymmetric Zn(3-ptz)<sub>2</sub> and Zn(OH)(3-ptz) MOFs with <i>in-situ </i>ligand formation. In acidic environments, we find that decreasing the amount of ligand below the stoichiometric molar ratio 1:2 also produces highly transparent single-crystal octahedrons of <b>Zn(3-ptz)<sub>2</sub></b>. In alkaline environments, we obtain long rod-like <b>Zn(OH)(3-ptz) </b>crystals whose length exceeds previous reports by up to four orders of magnitude. Potential applications of these results in the development of MOF-based nonlinear optical devices are discussed.

Single crystal to single crystal transformation of spin-crossover coordination polymers from 3D frameworks to 2D layers

2021 ◽  
Vol 9 (15) ◽  
pp. 5082-5087
Author(s):  
Yu Gong ◽  
Wang-Kang Han ◽  
Hui-Shu Lu ◽  
Qing-Tao Hu ◽  
Huan Tu ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Single Crystal ◽  
Coordination Polymers ◽  
Ligand Exchange ◽  
Spin Crossover ◽  
Metal Organic Frameworks ◽  
Crystal Transformation ◽  
Metal Organic

New Hofmann-type metal–organic frameworks display rare and complete ligand exchange induced single crystal to single crystal transformations from 3D frameworks to 2D layers, accompanied by magnetic properties transition from two-step SCO behavior to hysteretic SCO behavior.

Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

2020 ◽  
Vol 75 (8) ◽  
pp. 727-732
Author(s):  
Chen Zhang ◽  
Jian-Qing Tao
Keyword(s):  
Crystal Structure ◽  
Thermal Analysis ◽  
Uv Light ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
X Ray Diffraction ◽  
X Ray ◽  
Uv Light Irradiation ◽  
Photocatalytic Activities ◽  
Metal Organic

AbstractA new Cu(II) metal-organic framework, [Cu(L)(OBA)·H2O]n (1) [H2OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1H-benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (44·62) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.

From Ru nanoparticle-encapsulated metal–organic frameworks to highly catalytically active Cu/Ru nanoparticle-embedded porous carbon

2017 ◽  
Vol 5 (10) ◽  
pp. 4835-4841 ◽  
Author(s):  
Pradip Pachfule ◽  
Xinchun Yang ◽  
Qi-Long Zhu ◽  
Nobuko Tsumori ◽  
Takeyuki Uchida ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
High Temperature ◽  
Porous Carbon ◽  
Metal Organic Frameworks ◽  
Ammonia Borane ◽  
Carbon Composites ◽  
High Catalytic Activity ◽  
Catalytically Active ◽  
Metal Organic

High-temperature pyrolysis of Ru nanoparticle-encapsulated MOF (Ru@HKUST-1) afforded ultrafine Cu/Ru nanoparticle-embedded porous carbon composites (Cu/Ru@C), which show high catalytic activity for ammonia borane hydrolysis.

A series of microporous and robust Ln-MOFs showing luminescent properties and catalytic performances towards Knoevenagel reactions

2021 ◽  
Author(s):  
Qing-Xia Yao ◽  
Miaomiao Tian ◽  
Jun Zheng ◽  
Jintang Xue ◽  
Xuze Pan ◽  
...  
Keyword(s):  
Single Crystal ◽  
Metal Organic Frameworks ◽  
Luminescent Properties ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
Catalytic Performances

A series of microporous Ln(III)-based metal-organic frameworks (1-Ln) have been hydrothermally synthesized by using 4,4',4''-nitrilotribenzoic acid (H3NTB). Single crystal X-ray diffraction analyses show 1-Ln are isostructural and have 3D porous...

scholarly journals Synthesis, Crystal Structure, and Luminescent Properties of New Zinc(II) and Cadmium(II) Metal-Organic Frameworks Based on Flexible Bis(imidazol-1-yl)alkane Ligands

Crystals ◽  
2016 ◽  
Vol 6 (10) ◽  
pp. 132 ◽  
Author(s):  
Marina Barsukova ◽  
Tatiana Goncharova ◽  
Denis Samsonenko ◽  
Danil Dybtsev ◽  
Andrei Potapov
Keyword(s):  
Crystal Structure ◽  
Metal Organic Frameworks ◽  
Luminescent Properties ◽  
Metal Organic
Sign in / Sign up

Export Citation Format

Share Document